Phase transition in porous electrodes

It is shown by Monte Carlo simulation that electrochemical thermodynamics of electrolytes in a porous electrode is qualitatively different from that in the bulk with a planar electrode. In particular, first order phase transitions occur in porous electrodes when the pore size is comparable to the ion size of the electrolytes: as the voltage is increased from zero, the surface charge density and the ion density in the porous electrodes discontinuously change at a specific voltage. The critical points for those phase transitions are identified.     

水蒸气沉淀法制备SiO2/偏氟乙烯-六氟丙烯共聚物复合微孔型聚合物电解质的研究

用水蒸气沉淀法制备了SiO2 偏氟乙烯 六氟丙烯共聚物 [P(VDF HFP) ]复合微孔型聚合物电解质 ,并研究了纳米SiO2 的加入对微孔结构及复合微孔型聚合物电解质性能的影响 .SEM观察发现当纳米SiO2 的添加量大于 0 1倍聚合物质量时 ,可以在微孔中观察到纳米粒子的严重团聚现象 .电导率的测量表明添加 0 0 5倍聚合物质量的纳米SiO2 后 ,微孔型聚合物电解质的电导率有明显提高 ,但进一步增大添加量后 ,电导率有所下降 .另外 ,实验发现添加纳米SiO2 可以明显提高微孔型聚合物电解质与锂金属电极之间的界面稳定性 ,特别是添加量为 0 0 5倍聚合物质量时的效果良好 .     

Gate Tunable Organic Light Emitting Diodes: Principles and Prospects

This record summarizes our recent developments on gate‐tunable organic light‐emitting diodes (OLEDs). The key point is to modulate the charge carrier injection barrier by the applied gate potential. One way is to electrochemically dope charge carrier injection layer through porous electrodes. The electrochemically doped charge carrier layer thus form gate‐tunable contact with porous electrodes. Another way is to modulate the work‐function of electrodes that can have varied charge carrier injection barriers following the applied gate potential. Gate‐tunable OLEDs based on these two working principles have been fabricated, characterized and demonstrated for displaying simple digitals and letters. New materials including dielectric, porous electrodes, work function tunable electrodes, and charge carrier injection materials have been further explored for performance improvement.     

氢氧化钾活化制备超级电容器多孔碳电极材料

具有高比表面积、良好导电性的多孔碳材料在超级电容器中有着广泛的应用前景. 大量的研究工作致力于通过物理或者化学手段合成并调控多孔材料的微观结构. 在众多多孔碳材料的制备方式中,氢氧化钾作为一种高效的活化剂,常用于制备具有良好孔径分布和高比表面积多孔碳电极材料. 本文主要结合作者课题组的研究工作,着重概述利用氢氧化钾活化sp²碳纳米材料制备多孔碳材料的机理过程、结构形貌的转变以及所得材料的电化学性能,希望对发展新型的高性能基多孔碳材料的超级电容器电极材料有所帮助.     

甲醛电化学传感器多孔气体扩散电极不同催化层结构与响应性能研究

多孔气体扩散电极的制备是制备甲醛电化学传感器的关键所在, 其中催化层的结构直接影响到传感器的响应性能. 通过柠檬酸三钠还原法合成了纳米金-活性炭、纳米金-碳纳米管催化剂, 制备了甲醛电化学传感器多孔气体扩散电极, 并对电极进行SEM(扫描电子显微镜)物理表征. 在甲醛气体浓度为0.24和0.63 mg/m³时, 电极C具有较好的响应, 在0.1到0.84 mg/m³浓度范围内, 线性方程为y＝10.515x＋4.4049 (R²＝0.9917), 响应时间约80 s. 分析了不同催化剂的气体扩散电极结构与甲醛响应性的关系, 为研制开发性能优良的甲醛电化学传感器奠定了基础.     

Carbon Aerogel Films Synthesized at Ambient Conditions

Carbon aerogels derived from organic sol-gel process and supercritical drying are novel porous materials with interconnect structures and higher electrical conductivity, which are considered to be ideal electrode materials for supercapacitors and rechargeable batteries. The objective of the research was to synthesize carbon aerogel films at ambient conditions. Resorcinol formaldehyde (RF) and carbon aerogel films have been produced with extremely high RC ratio (molar ratio of resorcinol to catalyst) followed by subcritical drying. The structure of the porous films was investigated using electron scanning microscope. The specific surface area was measured by using nitrogen adsorption (BET) and electrical conductivity was measured with four-probe method. It was found that with extremely high RC ratio, the porous structure of RF and carbon aerogel films can be controlled from micro to macro porous at ambient conditions. With respect to the application as electrodes for fuel cells, carbon aerogel films with different porous structures on the two surfaces have been also obtained through optimizing the sol-gel process.     

Electrodeposition and lithium storage performance of novel three-dimensional porous Fe–Sb–P amorphous alloy electrode

The three-dimensional porous Fe–Sb–P amorphous alloy electrodes were prepared by electroplating on porous copper current collector. The structure and electrochemical performance of the electroplated Fe–Sb–P amorphous alloy electrodes have been investigated in detail. XRD results showed that the as-deposited Fe–Sb–P alloy electrode exhibits an amorphous nature. Electrochemical tests indicated that at the 50th cycle, the Fe–Sb–P amorphous alloy electrodes can deliver a discharge capacity of 448 mAh g^?1. The porous and amorphous structure of electrode of Fe–Sb–P alloy was beneficial in relaxing the volume expansion during cycling, which improved the cycle ability of Fe–Sb–P alloy electrode.     

锌银电池中氧化银电极的光电化学研究

用光电化学方法研究棒状和多孔氧化银电极在阳极极化过程中的光响应规律可以得到许多信息。最大光响应出现在电极表面的AgO被充分地还原为Ag_2O以及Ag结晶即将生成瞬间, 多孔电极和实体电极开路光电位ΔV_(ph,oc)之比有助于对多孔电极孔结构的了解, 首次观测到n-p-n光响应波形的转化。     

Crack‐Free Periodic Porous Thin Films Assisted by Plasma Irradiation at Low Temperature and Their Enhanced Gas‐Sensing Performance

Homogenous thin films are preferable for high‐performance gas sensors because of their remarkable reproducibility and long‐term stability. In this work, a low‐temperature fabrication route is presented to prepare crack‐free and homogenous metal oxide periodic porous thin films by oxygen plasma irradiation instead of high temperature annealing by using a sacrificial colloidal template. Rutile SnO₂ is taken as an example to demonstrate the validity of this route. The crack‐free and homogenous porous thin films are successfully synthesized on the substrates in situ with electrodes. The SnO₂ porous thin film obtained by plasma irradiation is rich in surface OH groups and hence superhydrophilic. It exhibits a more homogenous structure and lower resistance than porous films generated by annealing. More importantly, such thin films display higher sensitivity, a lower detection threshold (100 ppb to acetone) and better durability than those that have been directly annealed, resulting in enhanced gas‐sensing performance. The presented method could be applied to synthesize other metal oxide homogenous thin films and to fabricate gas‐sensing devices with high performances.     

3D-printed porous electrodes for advanced electrochemical flow reactors: A Ni/stainless steel electrode and its mass transport characteristics

Porous electrodes have shown high performance in industrial electrochemical processes and redox flow batteries for energy storage. These materials offer great advantages over planar electrodes in terms of larger surface area, superior space time yield and enhanced mass transport. In this work, a highly ordered porous stainless steel structure was manufactured by 3D-printing and coated with nickel from an acidic bath by electrodeposition in a divided rectangular channel flow cell. Following the electrodeposition, the volumetric mass transport coefficient of this electrode was determined by the electrochemical reduction of 1.0×10⁻³ mol dm⁻³ of ferricyanide ions by linear sweep voltammetry and chronoamperometry. The convection diffusion characteristics are compared with other geometries to demonstrate the novelty and the advantages of 3D-printed porous electrodes in electrochemical flow reactors. Robust porous electrodes with tailored surface area, composition, volumetric porosity and flow properties are possible.     

Fundamentals of lead-acid cells: Part XII. The reduction of lead sulphate

The reduction of lead sulphate grown anodically on planar and porous electrodes has been studied by a potentiostatic step technique. Both “planar” and “porous” electrodes behave in a similar manner and indicate that the electrode reduction reaction has a finite depth of penetration into the electrode. The kinetics of the formation of metallic lead on both electrodes appear to be instantaneous nucleation and two-dimensional growth processes with subsequent current limitations due to overlap and lead sulphate depletion. The current limitation processes are very complex and it has not been found possible to fit a satisfactory mathematical model.     

CeO2—TiO2复合纳米晶多孔膜的光电化学行为

用溶胶凝胶法制备了CeO2－TiO2复合纳米晶多孔膜电极，并用XRD及原子力显微镜（AFM）进行表征．通过光电化学研究，发现了CeO2-TiO2复合纳米晶电极光响应的p型和n型转换现象．结果表明，随着CeO2含量的不同及外电场的变化，CeO2－TiO2复合纳米晶电极可以呈现不同的光响应．     

直接甲醇燃料电池纳米结构电催化材料及多孔电极研究

直接甲醇燃料电池(DMFC)因其燃料能量密度高,工作温度低,低污染排放等优点被认为是用作移动设备电源的最佳选择之一,至今已有美国的Oorja Protonics公司和丹麦的IRD公司等新能源相关企业相继发布了多款用于手机、电脑、通信基站、叉式装卸机或房车的商业产品.然而, DMFC内部的复杂情况造成的多种不同的电压损失仍旧使得其实际电压效率远低于理论值.其中从阳极渗透到阴极的甲醇造成的混合电位导致的电压损失尤为明显.目前,众多研究人员都致力于开发高稳定性、高耐久性、高性能且低成本的催化材料体系,以克服传统Pt催化剂存在的各种问题.除了催化剂本身之外, DMFC的问题还与其中膜电极的微结构和电化学特性息息相关.膜电极是化学能通过电催化氧化还原反应转化为电能的反应场所,通常由阳极扩散层、阳极催化层、质子交换膜、阴极催化层和阴极扩散层依序组合而成.通过对MEA中的各层进行优化,如传质管理和甲醇渗透等问题都能得到有效解决.
　　近年来,纳米技术常被用于改进DMFC性能的研究.具备纳米结构的金属-碳/金属氧化物载体类催化材料得到了广泛研究.这些电催化材料在制备方法、结构和组分上都有较大区别.结构方面,许多研究都证明制备纳米级多孔网络结构或者有序阵列结构的催化层有助于提高催化性能和Pt的利用率.组分方面,许多研究人员都开展了引入Pt以外金属成分或金属氧化物来改变Pt催化剂的表面电子状态的研究.引入这些组分导致的配位体效应可以通过弱化Pt与H+, OH-或COads等的相互作用来起到抗催化毒化和提高催化效率的作用.尽管对于DMFC领域的认知逐渐完善,但是仍有许多问题有待解决.因此,本文介绍了目前用于DMFC的纳米结构电催化材料和多孔电极的研究进展.重点介绍了纳米结构催化剂和载体材料的合成及表征.
　　通过对比不同催化材料的特性可以发现,在本文涉及到的催化材料中, In0.1SnO2-Pt和(MoO3)0.2SnO2-Pt/C表现出了最高的催化活性,但是它们高效催化甲醇电氧化所需的碱性环境与现在占绝对主流地位的Nafion质子交换膜所必须的酸性环境相冲突,所以其实际应用价值在碱性阴离子交换膜研究取得突破前都难以有效发挥.而另一类表现较好的采用溶致液晶模板法合成的纳米树枝状和纳米星形Pt催化剂则存在制备工艺难以商业规模化的问题.总的来说,采用溶剂热合成法制备的Pt-NRCeO2/GNs和Pt/Ti0.9Sn0.1O2-C等纳米结构金属氧化物、碳材料复合载体和Pt基贵金属催化剂组成的催化材料体系不仅催化性能相对于商业化Pt纳米颗粒有很大提高,而且制备方法易于商业规模化,值得进一步关注.此外,本文还介绍了如内部传质过程的理论建模计算和膜电极中功能结构的制备等优化DMFC中多孔电极内传质过程的方法.通过计算机模拟得到优化DMFC内部传质过程所需的扩散层、催化层的传质特性相关参数,再通过改进MEA制备工艺,有效控制各层的结构参数向模拟的优化值靠拢,能够实现DMFC性能的有效提升.综合模拟、实验研究及工艺研究结果,根据实际需要,设计和制备包含新功能层的MEA的相关研究也更进一步提高了DMFC的性能和实用性.就目前的研究情况而言,如果在性能提升的基础上,使用寿命再取得突破, DMFC一定会有很好的商业应用前景.     

Electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH) at thick-film gold electrodes

Cyclic voltammetric and electrochemical impedance spectroscopic investigations of screen-printed, thick-film gold electrodes reveal significant differences when compared with conventional polished gold disk electrodes of comparable size. The rough and porous structure of the thick-film electrode surface leads to an actual electrode area which is increased six-fold compared to polished disk electrodes. Due to the catalytic properties of these surface structures it is possible to perform the electrochemical oxidation of reduced nicotinamide adenine dinucleotide (NADH) at relatively low overpotentials, i.e. +0.145 V vs. SCE. By operating electrodes at this potential, electrode fouling processes and interference from electroactive species, e.g. acetaminophen, are minimized. An amperometric glucose sensor based on polymer matrix-entrapped glucose dehydrogenase with a working potential of +0.145 V vs. SCE was successfully incorporated into a flow injection analysis (FIA) system.     

Energy Storage Materials from Nature through Nanotechnology: A Sustainable Route from Reed Plants to a Silicon Anode for Lithium‐Ion Batteries

Silicon is an attractive anode material in energy storage devices, as it has a ten times higher theoretical capacity than its state‐of‐art carbonaceous counterpart. However, the common process to synthesize silicon nanostructured electrodes is complex, costly, and energy‐intensive. Three‐dimensional (3D) porous silicon‐based anode materials have been fabricated from natural reed leaves by calcination and magnesiothermic reduction. This sustainable and highly abundant silica source allows for facile production of 3D porous silicon with very good electrochemical performance. The obtained silicon anode retains the 3D hierarchical architecture of the reed leaf. Impurity leaching and gas release during the fabrication process leads to an interconnected porosity and the reductive treatment to an inside carbon coating. Such anodes show a remarkable Li‐ion storage performance: even after 4000 cycles and at a rate of 10 C, a specific capacity of 420 mA h g^?1 is achieved.     

DSA-type anode based on conductive porous p-silicon substrate

Porous silicon (PS) thin films have been prepared by electrochemical anodization of p-Si in HF–H₂O–EtOH solution and they have been used as substrate material for the preparation of iridium oxide based electrodes (PS/IrO₂) using the thermal decomposition technique. The morphology and the electrochemical behaviour of the PS/IrO₂ have been studied and the results have been compared with IrO₂ electrodes deposited on a sandblasted p-silicon (p-Si/IrO₂). SEM analyses have revealed that the PS/IrO₂ electrodes are porous, rough and IrO₂ appears to be deposited within some silicon pores, while the p-Si/IrO₂ present a ‘mud-cracked’ surface. Cyclic voltammetries in 1 M HClO₄ have shown that the PS/IrO₂ presents higher surface area than p-Si/IrO₂.     

Phase transition in porous electrodes. II. Effect of asymmetry in the ion size

The electrochemical thermodynamics of electrolytes in porous electrodes is qualitatively different from that in the bulk with planar electrodes when the pore size is comparable to the size of the electrolyte ions. In this study, the effect of the ion size asymmetry on the thermodynamics in porous electrodes was studied by using Monte Carlo simulation. We used the electrolyte ions for which the size of the cations and that of anions is different. Due to the asymmetry in the ion size, the ionic structure and the way the surface charge is distributed on the electrode surfaces were found to be qualitatively different in the cathode and in the anode. In particular, for some ranges of applied voltage, the distribution of the surface charge induced on the electrode planes shows inhomogeneity, which is not intrinsic to the structure of the porous electrodes. The transition from the homogeneous to the inhomogeneous distribution of surface charge on changing the voltage is a second order phase transition.     

Powder Microelectrodes Applied to NO_2 Detection

TheelectrochemicalbehaviorsandthedetectionofNO2-haveattractedincreasingattentionrecentlybecauseoftheimportantrolesplayedbyNO2-inenvironmentandlifeprocesses.Thus,advancedtechniquesforthedetermination,especiallyon-sitedetermination,ofthenitriteinfoods...     

Application of Ion-Selective Electrodes as Reference Electrodes

Abstract

Reference electrodes limiting interfering effects of conventional reference electrodes on the measurement involving ion-selective electrodes have been developed. They are constructed of a plastic body with porous plug or sleeve junction. Solid state, low impedance, ion-selective electrodes (cupric, cadmium, fluoride) in the equilibrium of corresponding ion solution are used as the half-cells. The absence of interfering ions in the electrolyte allows the determination of the ion of interest at extremely low levels without interference. The electrodes have good reproducibility and stable intercomparison potentials of ± 0.2 mV. The performance of the electrodes has been tested for the measurement of sub-ppm halide levels. Data on stability, reproducibility, effects of temperature, ionic strengthand pH is presented and compared to that of conventional reference electrodes.     

不同浸润性多孔电极表面的气泡行为

采用氢气模板法制备了具有多孔结构的电极; 通过改变电镀电流密度和电镀时间实现了电极表面多孔结构孔径和分布的控制; 通过改变表面化学组成有效调控了电极表面的浸润性质. 比较了具有不同微观结构和表面化学组成的电极在给定条件下电解水过程中气泡的产生及行为机制. 实验结果表明: 相对于亲水的多孔电极, 疏水的多孔电极表面能够黏附气泡, 更易倾向于形成稳定的气膜; 多孔结构对于亲水电极表面气泡行为的影响比对疏水电极表面气泡行为的影响更为显著; 与没有多孔结构的亲水电极相比, 具有多孔结构的亲水电极表面产生的气泡数量多, 速率快; 与较小孔径的多孔亲水电极相比, 较大孔径的多孔亲水电极表面产生气泡速率快且黏附气泡数量少. 该研究结果为微气泡减阻电极的设计提供了理论依据.